Suenne Kim

Nanoscale Tunable Reduction of Graphene Oxide for Graphene Electronics

Writing Conductive Lines with Hot Tips The interface within devices between conductors, semiconductors, and insulators is usually created by stacking patterned layers of different materials. For flexible electronics, it can be advantageous to avoid this architectural constraint. Graphene oxide, formed by chemical exfoliation of graphite, can be reduced to a more conductive form using chemical reductants. Wei et al. (p. 1373) now show that layers of graphene oxide can also be reduced using a hot atomic force microscope tip to create materials comparable to those of organic conductors. This process can create patterned regions (down to 12 nanometers in width) that differ in conductivity by up to four orders of magnitude. Conducting regions can be drawn on graphene oxide sheets with a heated atomic force microscope tip. The reduced form of graphene oxide (GO) is an attractive alternative to graphene for producing large-scale flexible conductors and for creating devices that require an electronic gap. We report on a means to tune the topographical and electrical properties of reduced GO (rGO) with nanoscopic resolution by local thermal reduction of GO with a heated atomic force microscope tip. The rGO regions are up to four orders of magnitude more conductive than pristine GO. No sign of tip wear or sample tearing was observed. Variably conductive nanoribbons with dimensions down to 12 nanometers could be produced in oxidized epitaxial graphene films in a single step that is clean, rapid, and reliable.

Room-temperature metastability of multilayer graphene oxide films.

Graphene oxide potentially has multiple applications. The chemistry of graphene oxide and its response to external stimuli such as temperature and light are not well understood and only approximately controlled. This understanding is crucial to enable future applications of this material. Here, a combined experimental and density functional theory study shows that multilayer graphene oxide produced by oxidizing epitaxial graphene through the Hummers method is a metastable material whose structure and chemistry evolve at room temperature with a characteristic relaxation time of about one month. At the quasi-equilibrium, graphene oxide reaches a nearly stable reduced O/C ratio, and exhibits a structure deprived of epoxide groups and enriched in hydroxyl groups. Our calculations show that the structural and chemical changes are driven by the availability of hydrogen in the oxidized graphitic sheets, which favours the reduction of epoxide groups and the formation of water molecules.

The interplay between apparent viscosity and wettability in nanoconfined water

Understanding and manipulating fluids at the nanoscale is a matter of growing scientific and technological interest. Here we show that the viscous shear forces in nanoconfined water can be orders of magnitudes larger than in bulk water if the confining surfaces are hydrophilic, whereas they greatly decrease when the surfaces are increasingly hydrophobic. This decrease of viscous forces is quantitatively explained with a simple model that includes the slip velocity at the water surface interface. The same effect is observed in the energy dissipated by a tip vibrating in water perpendicularly to a surface. Comparison of the experimental data with the model shows that interfacial viscous forces and compressive dissipation in nanoconfined water can decrease up to two orders of magnitude due to slippage. These results offer a new understanding of interfacial fluids, which can be used to control flow at the nanoscale.

Nonperturbative Chemical Modification of Graphene for Protein Micropatterning

Graphenes extraordinary physical properties and its planar geometry make it an ideal candidate for a wide array of applications, many of which require controlled chemical modification and the spatial organization of molecules on its surface. In particular, the ability to functionalize and micropattern graphene with proteins is relevant to bioscience applications such as biomolecular sensors, single-cell sensors, and tissue engineering. We report a general strategy for the noncovalent chemical modification of epitaxial graphene for protein immobilization and micropatterning. We show that bifunctional molecule pyrenebutanoic acid-succinimidyl ester (PYR-NHS), composed of the hydrophobic pyrene and the reactive succinimide ester group, binds to graphene noncovalently but irreversibly. We investigate whether the chemical treatment perturbs the electronic band structure of graphene using X-ray photoemission (XPS) and Raman spectroscopy. Our results show that the sp(2) hybridization remains intact and that the π band maintains its characteristic Lorentzian shape in the Raman spectra. The modified graphene surfaces, which bind specifically to amines in proteins, are micropatterned with arrays of fluorescently labeled proteins that are relevant to glucose sensors (glucose oxidase) and cell sensor and tissue engineering applications (laminin).

Direct fabrication of arbitrary-shaped ferroelectric nanostructures on plastic, glass, and silicon substrates

A complementary metal-oxide-semico-nductor (CMOS)-compatible method for the direct fabrication of arbitrary-shaped Pb(Zr0.52 Ti0.48)O3 and PbTiO3 ferroelectric/piezoelectric nanostructures on plastic, silicon, and soda-lime glass substrates is reported. Thermochemical nanolithography is used to induce nanoscale crystallization of sol-gel precursor films. Ferroelectric lines with width ≥30 nm, spheres with diameter ≥10 nm, and densities up to 213 Gb in(-2) are produced.

Direct writing and characterization of poly(p-phenylene vinylene) nanostructures

We report the use of thermochemical nanolithography to convert a precursor polymer film to poly(p-phenylene vinylene) with sub-100 nm spatial resolution, in ambient conditions. The local thermochemical conversion is verified by Raman spectroscopy, fluorescence imaging, and atomic force microscopy. This convenient direct writing of conjugated polymer nanostructures could be desirable for the design and fabrication of future nanoelectronic, nanophotonic, and biosensing devices.

Parallelization of thermochemical nanolithography

One of the most pressing technological challenges in the development of next generation nanoscale devices is the rapid, parallel, precise and robust fabrication of nanostructures. Here, we demonstrate the possibility to parallelize thermochemical nanolithography (TCNL) by employing five nano-tips for the fabrication of conjugated polymer nanostructures and graphene-based nanoribbons.

Morphology dependence of radial elasticity in multiwalled boron nitride nanotubes

We report on the measurement of the radial modulus of boron nitride nanotubes (BN-NTs) with various sizes and thicknesses. These BN-NTs are radially much stiffer than previously reported thinner and smaller BN-NTs. Here, we show the key role of the morphology of the nanotubes in determining their radial rigidity; in particular, we find that the external and internal radii, Rext and Rint, have a stronger influence on the radial modulus than the nanotube’s thickness. The radial modulus decreases nonlinearly with 1/Rext until reaching, for a large number of layers and a large radius, the transverse elastic modulus of bulk h-BN.

Film Structure of Epitaxial Graphene Oxide on SiC: Insight on the Relationship between Interlayer Spacing, Water Content, and Intralayer Structure

Chemical oxidation of multilayer graphene grown on silicon carbide yields films exhibiting reproducible characteristics, lateral uniformity, smoothness over large areas, and manageable chemical complexity, thereby opening opportunities to accelerate both fundamental understanding and technological applications of this form of graphene oxide films. Here, we investigate the vertical inter-layer structure of these ultra-thin oxide films. X-ray diffraction, atomic force microscopy, and IR experiments show that the multilayer films exhibit excellent inter-layer registry, little amount (<10%) of intercalated water, and unexpectedly large interlayer separations of about 9.35 A. Density functional theory calculations show that the apparent contradiction of “little water but large interlayer spacing in the graphene oxide films” can be explained by considering a multilayer film formed by carbon layers presenting, at the nanoscale, a non-homogenous oxidation, where non-oxidized and highly oxidized nano-domains coexist and where a few water molecules trapped between oxidized regions of the stacked layers are sufficient to account for the observed large inter-layer separations. This work sheds light on both the vertical and intra-layer structure of graphene oxide films grown on silicon carbide, and more in general, it provides novel insight on the relationship between inter-layer spacing, water content, and structure of graphene/graphite oxide materials.

Effects of postnitridation annealing on band gap and band offsets of nitrided Hf-silicate films

The effects of film composition and postnitridation annealing on band gap and valence band offset were examined in nitrided Hf-silicate films prepared using direct plasma nitridation. Regardless of the composition of Hf-silicate films, the band gap characteristics were similar after direct plasma nitridation (4.5±0.1eV) and postnitridation annealing (5.6±0.1eV). The decrease in band gap after direct plasma nitridation was caused by the formation of Si–N and Hf–N bonds, while the recovery of band gap by postnitridation annealing was influenced by the dissociation of unstable Hf–N bonds. The difference in valence band offset was strongly related to the chemical states of Si–N bonds.